Process for deasphalting a petroleum feed oil for use in a hydrocracking zone



J. w. TETER ETAL 2,952,615 PROCESS FOR DEASPHALTING A PETROLEUM FEED OIL FOR USE IN A HYDROCRACKING ZONE Filed Aug. 5; 1955 Sept. 13,1960

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Ed? v o m 3 lA/l/E/VTORS JohnW.Teter William P. Het1inger,Jr.

w Donald K. Hedeen Walter F. Lorenc ATTOR Y United States Patent PROCESS FOR DEASPHALTING A PETROLEUM OR FOR USE IN A HYDRUCRACKING John W. Teter, Chicago, William P. Hetl'inger, Jr., Dolton, Donald K. Hedeen, Markham, and Walter F. Lorene, Harvey, 111., assignors to Sinclair Refining Company, New York, N.Y., a corporation of Maine Filed Aug. 5, 1955, Ser. No. 531,508

1 Claim. (Cl. 208-86) This invention relates to an improved method for the manufacture of gasoline, diesel fuels, gas oils and the like from petroleum residues such as topped crude, reduced crude and so forth.

It has heretofore been proposed to produce gasoline and other lighter petroleum products by hydrocracking petroleum residues. This has been accomplished by hydrogenating the residue in the presence of a suitable catalyst under conditions of temperature and pressure which result in cracking as well as hydrogenation. When this is done, however, the catalyst employed rapidly becomes inactive due to the deposition thereon of carbonaceous material. The catalyst must then be regenerated to restore it to its original or active condition, and this generally necessitates an interruption of the operation so that product quality is not uniform. At the same time, the amount of hydrogen consumed in the hydrogenation is relatively high.

In accordance with the present invention, a new method for the processing of petroleum residues has been devised. This method involves separating the petroleum residue, generally one having an initial boiling point above about 650 F., into two fractions. The first fraction comprises about 75 to 95 percent by weight of the material therein soluble in n-pentane according to AST M test D893-52T and having a content of materials insoluble in n-pentane not exceeding about 2 percent by Weight by the same test. The second fraction comprises the remainder of the residue. The first fraction is then hydrocracked while it is in contact with hydrogen and a hydrocracking catalyst under hydrocracking conditions of temperature and pressure.

When the method is practiced in this manner, not only does the catalyst require considerably less frequent regeneration, but at the same time the hydrogen consumption is relatively low, yet a very large fraction of the petroleum residue can be hydrocracked in order to produce the relatively more valuable lower boiling materials such as gasoline.

The following example sets forth various embodiments which fall within the scope of the present invention:

EXAMPLE East Chicago Velma asphalt produced as bottoms in the vacuum distillation of crude oil (22% based on crude) was extracted with a butane-pentane blend containing about 40 percent by volume of pentane, the operation being conducted by pumping the asphalt into an upper portion of an ext action tower and the butanepentane blend into a lower portion thereof. Treated 2,952,615 Patented Sept. 13, 1960 5:1. The characteristics of the asphalt feed and the stabilized deasphalted oil produced in the operation are set forth in Table I below. The deasphalted oil contained about 1.2 weight percent of pentane insolubles.

Insol. in naphtha-.. Insol. in 0014 Insol. in CS Penetration, 77 F Ring & Ball, F..-

The stabilized deasphalted oil was subjected to a hydrocracking procedure employing the equipment shown diagrammatically in the accompanying figure. The apparatus comprised a heated one inch Universal reactor 1 which contained the bed of hydrocracking catalyst. Void space above and below the catalyst bed was packed with 5 mm. solid glass beads. Glass wool plugs retained the catalyst particles in place. Lines 2 and 3 served to introduce the feed into the reactor, and from the reactor the products passed by means of line 4 to primary receiver 5. A stream of vapors passed overhead from the primary receiver by means of line 6 into water jacketed condenser 7. A portion of the gases which were not condensed in the condenser was recycled by means of lines 9, 10, 11 and 3 back into the reactor. Gases recycled by means of lines 9, 10 and 11 pass through ammonia scrubber 12 and drier 13. The remainder of the gases not condensed in the condenser was Withdrawn from the system by means of lines 14 and 15 and was collected. Fresh hydrogen was introduced into the reactor by means of lines 16, 17 and 11, the hydrogen a being deoxygenated by means of Deoxo tube 18. Liquid product produced in the primary receiver was collected in product receiver 19 and liquid product condensed in the condenser was collected in product receiver 20. Line 21 served as a means of collecting gases which were not condensed in the product receivers, and line 22 was employed for the purpose of introducing hydrogen sulfide at such times as the catalyst needed sulfiding.

The catalyst employed in the various tests was a commercially available cobalt oxide and molybdenum oxide on alumina catalyst which was ground to 20-60 mesh.

Examples of suitcuts rim

including ssure, feed, catalyst andthe like, and this tungsten,

-zircon1aabout 0.2

Also, although in the specific experiments the amount of hydrogen indard cubic d will dean be emcompounds of the des with the oxides or 43321191935 00 0 0m0 0 om5 2 2 F. and the reaction pressurewill be within bout 700 to .ilg; Weight hin the range from d, if desired.

from about molybdenum,

f the order of chromate) or mixtures of nickel oxide with tungsten or chromium oxides.

those expe Examples of such tungstate or thiodisposed on or careriments illustrate.

ally employed in the hydrocracking of heavy petroleum oils can be utilized accordance with the present process.

f the periodic table des'which are known Synthetic cracking catalysts of ilica, alumm' a f hydrogen introduced into Any of the catalysts convention lfi although 760-875 F., pressures of 600- hourly space velocities of 0.34- further variations in reaction temperight hourly space velocity are however, the reaction tempera- Mixtures of these materials or are nickel molybdate, tlmgstate hin the range from a as those skilled in the art will undercobalt, nickel, iron and tin and their oxides and sulfides.

ical, sually, the amount 0 the reaction zone will be within the range 500 standard cubic feet to about 20,000 stan reaction conditions employed,

Generally,

d/or aluminum combined with minor amounts of oxides of these metals which may or may not be act1vated as by acid treatment. Specific examples of su Table II .s.i.g. and weight 10.2 were utilized, 0.312 5 ature, pressure and we ge from about 400 to about 3,000 p.s space velocities wit er barrel of feed. Thehydrogen consume Suitable catalysts of this type are silicates or mixtures of silicates or mixtures of oxi to be cracking catalysts.

57822228878 0 0 0 L00 7 L3 0 L 1232.

present invention. Thus, reaction temperatures of 2400 p permissible. ture used will be wit about 1,000 the ran 10 hourly to about 20 can be utilize troduced into the reaction system was 0 about 3500 or 6000 standard cubic feet per barrel,

stand. U

feet p 20 pend upon the temperature, pre can vary widely, as the specific exp able catalytic ingredients are molybdenum, vanadium, chromium,

compounds or two or more of the oxides c 30 ployed. For example, mixtures or iron group metal oxides or su sulfides of group'VI left column 0 constitute very satisfactory catalysts. mixtures or compounds or .chromate (or thiomolybdate, th

These catalytic ingredients can be ried by known cracking catalysts of the solid refractory this type will generally be mixtures of hydrous oxides silicon with one or more of the oxides of magnesium, boron, aluminum, titanium or zirconium. Natural crackg catalysts of this type are usually silicates of magnesium an able solid refractory cracking catalysts are natural or synthetic fluoride-promoted alumina, silica-alumina, silicaall within the scope of the 7 magnesia,zirconia-silica, titania-s 23252244008 LL2 L0 000 %221 15 also is not crit 79868451382 L2 3 2 Q0 2 0 LL 33 ealed in place in a bronze 70193119703 0 LL0 0 0 5 6 swL 11 2 d with flow was then established.

f run tely.

hour, after erature was allowed to drop to 940- nd hydrogen was introduced. The g cobalt and molybdenum oxides to the sulfides resulted in a rise in tempera- F. below opion 0 ima A process run of de in order to ducts were collected in flasks with the off gases going through a series bmitted for mass The stabilized liquid product was heric pressure Was e reactor and the heat to the furly 30 crating conditions and the system was pressure hydrogen. Fresh hydroge ducts collected in the flasks and stabilized to remove the C -materi f approximately 5 standdreactor and recycling h were then collected confor a split into, C

the Dry Ice-acetone traps lts obtained in a series of Following this, feed stock was introduced at a predetermined. rate han A The liquid pro The temperature Was brought up ,000 F. The temperature was as from the gas sampler and wet 600-950 F. cut and bottoms.

but runs Nos. 12, 13 and 14 used the same batch of catalyst and totalled 18 hours approx into the pressurize eratures and rates and establish steady state The products whic acetone traps, gas sampler and wet test meter.

V modifications can be made in the procedures of the specific experiments described above to provide 000 F. and held there for one which the tem Run No.

nt on Feed (uncor- In operation, the reactor was s block furnace, a hydrogen rate 0 A sample of dry g gas overhead from the stabilizer were su spectrograph analysis.

Table H sets forth the resu runs. In those runs, fresh hydrogen at the rate of 3,000 standard cubic feet per barrel were fed and recycle gas Temp. F Pressure,

610G rtEcted): C1 C1--- 0 nC4.. 104-. K34"--- Cs-400 400-600 (100-950 F Bottoms-950 F.+.

100(Coke+95 5 H1 Consumed s.c.f.lbbl 10 1875 s.c.f. Ha/bbl. once through, 2500 s.c,f /bh1. recycle.

arious Nitrogen area.. m Total pore Volume Volume of pores greater t Average pore radius ard cubic feet per hour at atmosp established through th 950 F. The hydrogen was turned 011 a sulfide at atmospheric pressure exothermic reaction of convertin ture to approximately 1 then allowed to drop to approximate of the gas was started simultaneously. approximately two hours duration was ma stituted the oflicial run:

The wet gases condensed in were combined with the liquid pro then submitted to fractionation 400 F. true boiling point gasoline, 400-600 F. true at the rate of 4,000 standard cubic feet per barrel were introduced into the reactor, with the except No. 11. Most of the data were obtained on runs of 8 WHsV.--

Products:

Percent Conv.:

other embodiments which'f S d n u m n .W a w m m d mtm Sm h P mo. CAP

nace was turned on. to about 1,

line out temp conditions.

of Dry Iceboiling point gas oil,

hours or less,

silica, alumina-boria-silica or alumina-magnesia-silica cracking catalysts. The catalytic ingredients can be dispersed on or composited with the base in any conventional manner, for example by impregnating it with a suitable solution of a salt followed by drying and calcining to convert the salt to the oxide.

The process of the present invention requires in the hydrogen step the use of a particular type of feed, namely, one prepared by separating a petroleum residue into two fractions, the first of which is hydrogenated and which has a content of materials insoluble in n-pentane not exceeding about 2 percent by weight. The fraction hydrogenated can be produced by extracting the residue countercurrently in a tower at a top temperature of ZOO-450 F. and a bottom temperature of 150 400 F. using a C -C parafiin, or mixture of such parafins, at a solvent to oil ratio of 3:1 to :1 by volume. The fraction subjected to hydrogenation can, if desired be produced by extracting an asphaltic residue countercurrently with a solvent mixture composed of 35 percent by volume of n-pentane in admixture with n-butane at a solvent to oil ratio of 7:1 by volume, top tower temperature of about 250 F., bottom tower temperature of about 210 F. and tower pressure of about 400 p.s.i.g. Lower solvent to oil ratios can also be utilized, for example, 5:=1.

In the specific experiments the hydrogenation was carried out with the catalyst disposed in a fixed bed. Other methods for contacting the feed, hydrogen and 6 catalyst can also be utilized, for example, the slurry system described in application Serial No. 531,507, filed August 5, 1955, now abandoned, in the names of John W. Teter, William P. Hellinger, Jr. and Calvin J. Bragg, wherein hydrogen, feed and powdered hydrocracking catalyst are fed into the bottom of a reaction vessel and a slurry of catalyst and hydrocracked oil are removed from the top of the reaction vessel. Also, if

. desired, a plurality of fixed beds of catalyst can be used.

It is claimed:

A method for the hydrocracking of hydrocarbon mixtures which comprises separating from a petroleum asphaltic residue produced as bottoms in the vacuum distillation of petroleum crude oil a fraction comprising about to percent by weight of the material therein soluble in n-pentane and having a content of materials insoluble in n-pentane not exceeding about 2 percent by weight and thereafter subjecting said fraction to hydrocracking conditions of temperature and pressure while in contact with a hydrocracking catalyst.

References Cited in the file of this patent UNITED STATES PATENTS 2,055,135 Pier et a1 Sept. 22, 1936 2,149,900 Pier et al Mar. 7, 1939 2,697,681 Murray et a1. Dec. 21, 1954 2,700,637 Knox Jan. 25, 1955 2,783,188 Agoston Feb. 26, 1957 

